Note: Descriptions are shown in the official language in which they were submitted.
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SPECIFICATION
Metal-Processing Oil composition and Metal-Processing Method
Technical Field
The present invention relates to a water-soluble metal-processing oil
composition which can widely be applied to metal-processing methods including
cutting and grinding processing methods and even plastic forming methods and a
method for processing metals which makes use of the metal-processing oil
composition and more particularly to a water-soluble metal-processing oil
composition excellent in putrefaction resistant properties and a method for
processing metals which makes use of the metal-processing oil composition.
Background Art
There have been known, as cutting oils (or lubricants for cutting
processing) widely used in the fields of cutting and grinding processing,
water-
insoluble cutting oils which comprise a mineral oil as a base oil, and water-
soluble cutting oils which comprise, for instance, a mineral oil, a surfactant
and
an organic amine and which are diluted with water before use.
In this connection, a compound, called preservative, is added to water-
soluble cutting oil or an amine having a preservative effect is incorporated
into
the cutting oil, in order to improve the putrefaction resistant properties of
the
cutting oil.
However, there have recently been required further saving of natural
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resources of the earth and the prevention of any deterioration of global
environment and there has also been desired, even in the field of cutting
oils, for
the development of a cutting oil or a lubricant which is less harmful to
global
environment and which can further be used over a longest possible extended
period of time, as compared with the conventionally developed oils.
As such water-soluble metal-processing oils, there have conventionaIly
been known, for instance, a water-soluble metal-processing cutting oil
composition which makes use of Mentha (peppermint) oil (see Patent Document
1); a water-soluble metal-processing cutting oil composition which makes use
of
cinnamon oil (see Patent Document 2); a water-soluble metal-processing cutting
oil which makes use of an aromatic amine or an alicyclic amine (see Patent
Document 3); a water-soluble metal-processing cutting oil which makes use of a
benzole compound and a p-oxybenzoic acid ester compound (see Patent Document
4); an anti-bacterial water-soluble cutting oil which makes use of an alkylene-
diamine (see Patent Document 5); a water-soluble cutting oil composition which
makes use of a fatty acid alkanolamide-ethylene oxide adduct and an alkylamine-
ethylene oxide adduct, an alicyclic amine-ethylene oxide adduct, a fatty acid-
higher alcohol adduct (see Patent Document 6); a water-soluble
cutting/grinding
oil which makes use of, for instance, a primary, secondary or tertiary
alkylamine,
an aromatic diamine-oxyalkylene adduct, and an alicyclic diamine-oxyalkylene
adduct (see Patent Document 7); and such a water-soluble metal-processing
cutting oil composition which comprises a primary alkanolamine, a carboxylic
acid having 6 to 24 carbon atoms and a specific alkylene-diamine (see Patent
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Document 8).
However, these water-soluble metal-processing cutting oils are effective for
controlhng general bacteria, but do not show any sufficient effect on fungi
and
yeast. In this respect, those effective to control fungi and yeast make use of
a
halogen-containing compound, a polycyclic aromatic compound, a phenolic
compound or a metal salt, some of these compounds are specified to be subjects
for the PRTR (pollutant release and transfer register) regulation or control
and
they may adversely affect human body.
From the foregoing standpoints, the inventors of this invention have
conducted further investigations of main components (raw materials) used in
cutting oils and as a result, they have found that substances showing
putrefaction resistant properties such as preservatives and amines suffer from
the following problems:
As typical compounds serving as such preservatives, there can be listed,
for instance, chlorine atom-containing compounds, bromine atom-containing
compounds, fluorine atom-containing compounds. The metal-processing oils in
general generate waste oils after practically using the same. In this
connection, if
the waste oil is disposed, for instance, through combustion, the incinerator
would
be damaged by the action of gases generated through the combustion of waste
oil
such as chlorine gas or hydrogen chloride gas and this would correspondingly
lead to considerable reduction of service life of the incinerator. In
addition, it has
been recognized that a part of such chlorine atom-containing additive would
result in generation of dioxin through or during the foregoing incineration
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treatment.
On the other hand, there has been a strong movement to hold the use of
amines since some of them would be considered to be quite harmful to human
body. For instance, monoethanolamine which is specified as a substance to be
regulated on the basis of the provisions stipulated in the PRTR law and
enforced
since last year and secondary amines may have a high probability of generating
nitrosamines which serve as carcinogenic substances when they are used in
combination with a nitrite.
However, preservatives or amines have been considered to be essential
compounds to improve putrefaction resistant properties of cutting oils.
Patent Document 1: Japanese Patent No. 2,676,056;
Patent Document 2: Japanese Patent No. 2,645,675;
Patent Document 3= Japanese Patent No. 2,510,233;
Patent Document 4= Japanese Examined Patent Publication Hei 7-37632;
Patent Document 5: Japanese Examined Patent Publication Hei 7-30348;
Patent Document 6: Japanese Examined Patent Publication Hei 6-31388;
Patent Document 7: Japanese Un-Examined Patent Publication Hei 9-316482;
and
Patent Document 8= Japanese Examined Patent Pubhcation Hei 6-76590.
Disclosure of the Invention
Problems That the Invention is to Solve
It is an object of the present invention to provide a water-soluble metal-
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processing oil composition which can widely be applied to metal-processing
operations including cutting and grinding processing operations and even
plastic
forming operations and a method for processing metals which makes use of the
metal-processing oil composition. More particularly, it is an object of the
present
invention to provide a water-soluble metal-processing oil composition
excellent in
putrefaction resistant properties and a method for processing metals which
makes use of the metal-processing oil composition.
It is another object of the present invention to provide a water-soluble
metal-processing oil composition which is excellent in putrefaction resistant
properties and sparingly has any bad influence upon global environment and
human body and a method for processing metals which makes use of the metal-
processing oil composition.
Means for Solving the Problems
The inventors of this invention have conducted various studies to
accomplish the foregoing objects, have found that when a specific amine is
incorporated into a metal-processing oil composition in a specific rate as a
substitute for conventionally used preservative or amine, the resulting metal-
processing oil composition shows putrefaction resistant properties superior to
that observed for the cutting oil comprising the conventional preservative or
amine and have thus completed the present invention. Accordingly, the present
invention provides a water-soluble metal-processing oil composition and a
method for processing metals which makes use of the metal-processing oil
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composition as will be detailed below:
1. A metal-processing oil composition comprising an amine carrying a
linear or branched alkyl group having not less than 4 carbon atoms (component
A) in an amount ranging from 0.5 to 20% and an amine carrying a cycloalkyl
ring
or a benzene ring (component B) in an amount ranging from 0.5 to 20%.
2. The metal-processing oil composition as set forth in the foregoing item
1, wherein the component A is represented by the following general formula 1:
General Formula 1:
R' \N R3
/
RZ
wherein R' represents an alkyl group having not less than 4 carbon atoms or an
oxyalkyl group having not less than 4 carbon atoms; R2 and R3 represent at
least
one member selected from the group consisting of groups represented by the
formula: (CH2XO)YH, H, alkyl groups each having not less than 4 carbon atoms
or
oxyalkyl groups each having not less than 4 carbon atoms; x is an integer
ranging
from 2 to 4 and y is 1 or 2.
3. The metal-processing oil composition as set forth in the foregoing item
1 or 2, wherein the component B is at least one member selected from amines
represented by the following general formulas 2 to 5:
General Formula 2:
R4
R7
N N
I I
R5 Rs
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General Formula 3 :
R8 R11
N N
I9 I I
R9 R10
General Formula 4:
0 R1Z
N
R13
General Formula 5=
R15
\N R17-N
R1s \R1a
wherein R4 to R" may be the same or different and represent H or (CH2XO)nH, x
is an integer ranging from 2 to 4 and n is an integer ranging from 1 to 3;
R12 and R13 may be the same or different and represent H or C6H11
(cyclohexyl group) or (CXH2xO)nH, x is an integer ranging from 2 to 4 and n is
an
integer ranging from 1 to 3;
R14 to R16 may be the same or different and represent H or (CXH2XO)nH,
x is an integer ranging from 2 to 4 and n is an integer ranging from 1 to 3;
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R1" represents a group: C,tH2,t, and x is an integer ranging from 2 to 4.
4. The metal-processing oil composition as set forth in any one of the
foregoing items 1 to 3, wherein the component A is an amine represented by the
foregoing general formula 1, wherein R' represents an alkyl group having 4 to
12
carbon atoms, R2 and R3 each represent at least one member selected from the
group consisting of (CxH2XO),,H, H and alkyl groups having 4 to 12 carbon
atoms,
x is an integer ranging from 2 to 4, and y is 1 or 2.
5. The metal-processing oil composition as set forth in any one of the
foregoing items 1 to 4, wherein the component A is an amine represented by the
foregoing general formula 1, in which R1 represents an alkyl group having 4
carbon atoms, R2 and R3 each represent at least one member selected from the
group consisting of (CXH2XO)yH, H and alkyl groups having 4 carbon atoms, x is
an integer ranging from 2 to 4, and y is 1 or 2.
6. The metal-processing oil composition as set forth in any one of the
foregoing items 1 to 5, wherein the component A is a secondary amine
represented by the foregoing general formula 1, in which R' represents n-butyl
or
t-butyl group, R2 represents a group : (CXH2XO)yH, R3 represents H, x is an
integer
ranging from 2 to 4, and y is 1 or 2.
7. The metal-processing oil composition as set forth in any one of the
foregoing items 1 to 6, wherein the component A is n-butyl monoethanolamine or
t-butyl monoethanolamine.
8. The metal-processing oil composition as set forth in any one of the
foregoing items 1 to 7, wherein the component B is an amine represented by the
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foregoirig general formula 2 or 3, in which R4 to R" may be the same or
different
and each represent H or (CXH2XO)nH, x is an integer ranging from 2 to 4 and n
is
an integer ranging from 1 to 3.
9. The metal-processing oil composition as set forth in any one of the
foregoing items 1 to 8, wherein the component B is an amine represented by the
foregoing general formula 2 or 3, wherein R4 to R" represent H.
10. The metal-processing oil composition as set forth in any one of the
foregoing items 1 to 7, wherein the component B is an amine represented by the
foregoing general formula 4.
11. The metal-processing oil composition as set forth in the foregoing item
10, wherein the component B is dicyclohexylamine.
12. The metal-processing oil composition as set forth in the foregoing item
10, wherein the component B is an amine represented by the general formula 4,
wherein R12 and R13 may be the same or different and each represent a group:
(CXH2XO)nH, x is an integer ranging from 2 to 4 and n is an integer ranging
from
lto3.
13. The metal-processing oil composition as set forth in the foregoing item
12, wherein the component B is an amine represented by the general formula 4,
wherein R12 and R13 may be the same or different and each represent a group:
(C2H4O)õH, and n is an integer ranging from 1 to 3.
14. The metal-processing oil composition as set forth in any one of the
foregoing items 1 to 7, wherein the component B is an amine represented by the
foregoing general formula 5.
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15. The metal-processing oil composition as set forth in the foregoing item
14, wherein the component B is an amine represented by the general formula 5,
wherein R14 to R16 may be the same or different and each represent H or
(C2H4O)nH, and n is an integer ranging from 1 to 3.
16. A method for processing a metal characterized in that the method
makes use of the metal-processing oil composition as set forth in any one of
the
foregoing items 1 to 15.
Effects of the Invention
The water-soluble metal-processing oil composition according to the
present invention shows excellent working characteristics in the metal
processing
steps including cutting and grinding processing operations. In addition, the
metal-processing oil composition is likewise excellent in putrefaction
resistant
characteristics and sparingly has any bad influence upon global environment
and
human body. The metal-processing oil composition of the present invention can
exert antibacterial effects not only on general bacteria, but also fungi such
as
mold and yeast due to synergistic effect observed when using a specific water-
soluble amine and a specific water-insoluble amine in combination and
accordingly, the metal-processing oil composition shows putrefaction resistant
effect considerably higher than that observed for conventional metal-
processing
oil composition.
Best Mode for Carrying Out the Invention
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The metal-processing oil composition (stock solution) of the present
invention is characterized in that it comprises, on the basis of the total
amount of
the composition, an amine carrying a linear or branched alkyl group having not
less than 4 carbon atoms (component A) in an amount ranging from 0.5 to 20%
(in this specification, the term "%" means "% by mass" unless otherwise
specified)
and an amine carrying a cycloalkyl ring or a benzene ring (component B) in an
amount ranging from 0.5 to 20%.
The amine carrying a linear or branched alkyl group having not less than
4 carbon atoms, as the component A, may be, for instance, n-butyl
monoethanolamine, n-butyl diethanolamine, di-n-butyl monoethanolamine, t-
butyl monoethanolamine, t-butyl diethanolamine, di-t-butyl monoethanolamine,
n-butyl monoisopropanolamine, n-butyl diisopropanolamine, di-n-butyl
monoisopropanolamine, t-butyl mono-isopropanolamine, t-butyl
diisopropanolamine, di-t-butyl monoisopropanolamine, n-octyl
monoethanolamine, n-octyl diethanolamine, di-n-octyl monoethanolamine, n-
lauryl diethanolamine, and di-n-lauryl monoethanolamine.
The amine carrying a cycloalkyl ring or a benzene ring, as the component
B, may be, for instance, 1,3-bisaminomethyl cyclohexane, 1,3-bisaminomethyl
cyclohexane- ethylene oxide adducts, 1,3-bisaminomethyl cyclohexane-propylene
oxide adducts, m-xylene-diamine, m-xylene-diamine-ethylene oxide adducts, m-
xylene-diamine-propylene oxide adducts, cyclohexylamine, di-cyclohexylamine,
cyclohexylamine -ethylene oxide adducts, cyclohexylamine-propylene oxide
adducts, cyclohexyl- ethylene diamine, cyclohexyl-propylenediamine, cyclohexyl-
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butylenediamine, cyclohexyl -ethylene diamine -ethylene oxide adducts,
cyclohexyl-
propylenediamine-ethylene oxide adducts, and cyclohexyl-butylenediamine-
ethylene oxide adducts. These amines may be used alone or in any combination
of
a plurality of these amines.
The metal-processing oil composition of the present invention comprises at
least one amine carrying a linear or branched alkyl group having not less than
4
carbon atoms (component A) and at least one amine carrying a cycloalkyl ring
or
a benzene ring (component B), as essential components. In this connection,
examples of the components A preferably used herein are n-butyl
monoethanolamine, and t-butyl monoethanolamine; and examples of the
components B preferably used herein are cyclohexyl propyldiamine,
dicyclohexylamine and cyclohexylamine-ethylene oxide adducts, and more
preferably, the combination of cyclohexyl propyldiamine with
dicyclohexylamine,
or the combination of cyclohexylamine-ethylene oxide adducts with
dicyclohexylamine.
The metal-processing oil composition of the present invention is
characterized in that it comprises the component A and the component B in a
specific mixing ratio. More specifically, the amount of the component A ranges
from 0.5 to 20%, preferably 0.5 to 15% and more preferably 2 to 8%; and the
amount of the component B ranges from 0.5 to 20%, preferably 0.5 to 15% and
more preferably 2 to 8%.
If the amount of the component A is less than 0.5% and/or that of the
component B is less than 0.5%, the resulting metal-processing oil composition
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does not show any desired putrefaction resistant characteristics.
On the other hand, if the amount of the component A exceeds 20% or that
of the component B exceeds 20%, the resulting metal-processing oil composition
has a strong stimulation to the skin and may become a cause of skin roughness-
generation and accordingly, the composition cannot suitably be used as a metal-
processing oil. For this reason, the upper limits of the components A and B
are
preferably not more than 15%, respectively.
Furthermore, the foregoing component A may comprise a single component
or a mixture of at least two components and the same is also true for the
component B.
In addition, the water-soluble metal-processing oil composition according
to the present invention may if necessary comprise other basic substances such
as water-soluble amines and/or caustic potash and caustic soda. For instance,
examples of such water-soluble amines include diethanolamine,
diisopropanolamine, triethanolamine, triisopropanolamine, methyl
diethanolamine, dimethyl ethanolamine, monoisopropanolamine, 2-amino-2-
methyl-l-propanol, 2-(2-aminoethoxy) ethanol, diethyl monoisopropanolamine,
N,N-di-n-propylamino-isopropanol, N,N-ethylenediamine-(diisopropanol), N,N-
ethylenediamine-(diethanol), mono-n-butyl diethanolamine, monoethyl
diisopropanol-amine, and diglycolamine, but other water-soluble amines or
inorganic alkalis may likewise be used in the present invention.
More specifically, preferably used herein are the combinations of the
foregoing water-soluble amines with, for instance, diglycolamine, methyl
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diethanolamine, monoisopropanolamine, 2-amino-2-methyl-1-propanol, and 2-(2-
aminoethoxy) ethanol, in order to maintain pH value of the composition at a
relatively high level.
In addition, the water-soluble metal-processing oil composition of the
present invention may if necessary comprise linear and/or branched saturated
fatty acids and/or dibasic acids and specific examples thereof include caproic
acid,
enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid,
dodecanoic acid, tridecanoic acid, pentadecanoic acid, heptadecanoic acid,
nonadecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid,
arachic
acid, behenic acid, isostearic acid, elaidic acid, oleic acid, linoleic acid,
linolenic
acid, hydroxy-lauric acid, hydroxy-myristic acid, hydroxy-palmitic acid,
hydroxy-
stearic acid, hydroxy-arachic acid, hydroxy-behenic acid, ricinoleic acid,
hydroxy-
octadecenoic acid, sebacic acid, dodecane-diacid, dodecyl succinic acid,
lauryl
succinic acid, stearyl succinic acid, isostearyl succinic acid, and dimeric
acids. In
addition to the foregoing, usable in the present invention also include, for
instance, fatty acids derived from naturally occurring fats and oils such as
those
derived from animals, fishes, plants and cereals.
Furthermore, the water-soluble metal-processing oil composition of the
present invention may if necessary comprise a base oil. Examples of such base
oils are mineral oils, polyol esters, fats and oils, polyglycols, poly(a-
olefins), a-
olefins, n-paraffins, iso-paraffins, alkyl-benzenes, and polyethers. These
base oils
may be used alone or in any combination of a plurality of different base oils.
Preferably used herein include, for instance, mineral oils, polyglycols, and
alkyl-
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benzenes.
The metal-processing oil composition of the present invention may if
necessary comprise a rust proofing agent, for instance, a fatty acid such as
lauryl
succinic acid, stearyl succinic acid, isostearyl succinic acid or dodecane
diacid,'
sulfonic acid salt such as sodium petroleum sulfonate; and a carboxylic acid
amide.
Moreover, the metal-processing oil composition of the present invention
may if necessary comprise a silicone-containing antifoaming agent, an
alcoholic
antifoaming agent, or a benzothiazole type anticorrosive for metals.
Further, the metal-processing oil composition of the present invention may
if necessary comprise a preservative such as benzo-isothiazoline and/or a
derivative thereof, sodium Omadine, and metal pyrithionates; and/or an
alkylamine represented by laurylamine and oleylamine and oxyethylene adducts
thereof as a preservative or a bacterium-controlling agent.
The metal-processing oil composition of the present invention is in general
used after diluting the same 5 to 200 times with water.
The present invention will hereunder be described in more detail with
reference to the following Examples.
In the following Examples (1 to 28), there were prepared metal-processing
oil compositions whose compositions (by mass) (the amounts of the ingredients
summed to 100 parts by mass for each composition) were detailed in the
following
Table 1 (Examples 1 to 8), Table 2 (Examples 9 to 16) and Table 3 (Examples 17
to 28):
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Table 1=
Component 1 2 3 4 5 6 7 8
A n-butyl 5 5 5 5 5
monoethanolamine
n-butyl 5
diethanolamine
t-butyl 5
monoethanolamine
n-octyl 2
monoethanolamine
B m-xylenediamine 3
m-xylenediamine 4
EO 2 mole adduct
1.3-bisaminomethyl 3
cyclohexane
dic clohex lamine 5 5 5 5 3 3 3 5
cyclohexylp ropyl 1 1 1 1
diamine
cyclohexylamine
EO 2 mole adduct
1
meth l diethanolamine 6 6 6 6 6 6 6 6
monoisoprop anolamine 2
elar onic acid 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5
neodecanoic acid 1 1 1 1 1 1 1 1
oleic acid 5 5 5 5 5 5 5 5
dodecane diacid 2 2 2 2 2 2 2 2
sorbitan monooleate 9 9 9 8 9 9 9 9
laurylamine 3 3 3 3 3 3 3 3
EO 7 mole adduct
oleyl alcohol 3 3 3 3 3 3 3 3
EO 2 mole adduct
mineral oil Re. Re. Re. Re. Re. Re. Re. Re.
water 10 10 10 10 10 10 10 10
Re.: remnant
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Table 2
Component 9 10 11 12 13 14 15 16
A n-butyl 6 5 15 3 3 3 3 3
monoethanoleamine
n-butyl
diethanolamine
3
t-butyl
monoethanolamine
n-octyl
monoethanolamine
B m-x lenediamine
m-xylenediamine
EO 2 mole adduct
1.3-bisaminomethyl 1 1 3
cyclohexane
dic clohex lamine 3 2 2 3 3 3 3 3
cyclohexylpropyl
diamine
cyclohexylamine 8
EO 2 mole adduct
methyl diethanolamine
monoiso ro anolamine
di 1 colamine 6 5 8 8 2 6 4
pelargonic acid 7 5 5 5 5 5 5
neodecanoic acid 4
oleic acid 6 5 6 1
castor oil fatt acid 5 6 6 6 6 6
castor oil fatty acid
polycondensate 9 6 6 16 10 10 10 10
(AV: 32)
dodecane diacid 2 1 2 2 3 3 3 3
sorbitan monooleate
laurylamine 2 2 1
EO 7 mole adduct
oleyl alcohol 1 3 3 3 3 3
EO 2 mole adduct
thiazoline preservative
mineral oil Re.
alk l benzene 20 20 30 30 30 30 30
polyglycol 5 5 5 5 5
water 5 Re. Re. Re. Re. Re. Re. Re.
Re.: remnant
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Table 3-1
Component 17 18 19 20 21 22
A n-butyl mono-ethanoleamine 5 5 5 22
n-butyl diethanolamine
t-butyl monoethanolamine
n-octyl monoethanolamine
B m-xylene diamine 6
m-xylenediamine
EO 2 mole adduct
1.3-bisaminomethyl
c clohexane
dic clohex lamine 5 5 10 5
cyclohex lpropyl diamine 1 1 1 1
cyclohexylamine 5
EO 2 mole adduct
methyl diethanolamine 6 6 6 6 6 6
monoiso ro anolamine 3.2 3.2 2.5 2.5
di 1 colamine
pelargonic acid 3.5 3.5 3.5 3.5 3.5 3.5
neodecanoic acid 1 1 1 1 1 1
oleic acid 5 5 5 5 9 9
castor oil fatty acid
castor oil fatty acid
polycondensate (AV : 32)
dodecane diacid 2 2 2 2 2 2
sorbitan monooleate 7 7 10 10 9 9
laur lamine EO 7 mole adduct 3 3 3 3 3 3
oleyl alcohol EO 2 mole adduct 3 3 3 3 3 3
thiazoline preservative 0.5 0.5
mineral oil Re. Re. Re. Re. Re. Re.
alkyl benzene
ol 1 col
water 10 10 10 10 10 10
Re.: remnant
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Table 3-2
Component 23 24 25 26 27 28
A n-butyl mono-ethanoleamine 3 3 3 22
n-butyl diethanolamine
t-butyl monoethanolamine
n-octyl monoethanolamine
B m-xylene diamine 6
m-xylenediamine
EO 2 mole adduct
1.3-bisaminomethyl 6
cyclohexane
dic clohex lamine 3 3 10 10 5
cyclohex lprop l diamine 1 1 1
cyclohexylamine EO 2 mole 5 5
adduct
methyl diethanolamine
mono-iso ro anolamine
di 1 colamine 10 10 10 8 8 8
pelargonic acid 5 5 5 5 5 5
neodecanoic acid
oleic acid 4 4 4
castor oil fatty acid 6 6 6 6 6 6
castor oil fatty acid 10 10 10 10 10 10
polycondensate (AV : 32)
dodecane diacid 3 3 3 3 3 3
sorbitan monooleate
laurylamine EO 7 mole adduct
oleyl alcohol EO 2 mole adduct 3 3 3 3 3 3
thiazoline preservative 0.5
mineral oil
alkyl benzene 30 30 30 30 30 30
ol 1 col 5 5 5 5 5 5
water Re. Re. Re. Re. Re. Re.
Re.: remnant
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Each of the foregoing compositions was inspected for putrefaction resistant
property, skin roughness-generation, dilution stability and cutting property
according to the following methods:
Test for Examining Putrefaction-Resistance
To 100 ml of each lubricant comprising each candidate composition diluted,
with water, to a concentration of 3%, there was added the following
putrefaction
solution so that the concentration thereof was set at 3%, the resulting
mixture
was subjected to shaking culture at 30 degrees C( C), and 150 rpm for 14 days
and then the viable count for each cultured mixture was determined.
Putrefaction Solution:
Putrefied and deteriorated emulsion type cutting solution: 50%
Trypt-Soy Culture Medium: 25%
Grape Sugar-Peptone Culture Medium: 25%
The putrefaction solution used herein was obtained by subjecting the
mixture of the foregoing components to aeration for 24 hours to thus activate
the
mixture.
Evaluation Standard:
The numbers of general bacteria, mold, yeast and anaerobic bacterial cells
as well as a degree of contamination were evaluated using SAN-AI Biochecker
(available from San-ai Oil Co., Ltd.).
= General bacteria and yeast were evaluated according to the following 8
criteria
as expressed in terms of the bacterial or fungal living cell number per unit
volume of the culture me(hum (1 ml): No; 103 cells>; 104 cells; 105 cells; 106
cells;
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10' cells; and 107cells<.
= General bacteria and yeast were also evaluated according to the following 4
criteria as expressed in terms of the degree of contamination: No; L(slight
degree); M (medium degree); and H (severe degree).
The standard (border line) for judging on whether each composition could
be acceptable or not was as follows: "No" for mold, yeast and anaerobic
bacteria;
and "l03 cells/ml>" for general bacteria.
Evaluation of Inhibition of Skin Roughness-Generation:
Each cutting oil containing each candidate composition was diluted two
times with water and a droplet of the resulting diluted solution was dropped
on a
patch test unit (FIN Chamber, available from Epitest Co., Ltd.), the latter
was
then applied onto a site on the upper arm of a panelist with the use of an
adhesive tape, followed by the judgment of the skin roughness-generation on
the
basis of the condition of the skin, to which the patch was applied, examined
after
allowing the patch to stand on the upper arm for 24 hours. This was evaluated
on
the basis of the sum of the results (score) observed for subjects (10 male
panelists) and according to the following evaluation criteria:
Evaluation Criteria:
Score 3= The skin turned red, with the formation of blisters and wheals;
Score 2: The skin turned red and was swollen;
Score 1= The skin slightly turned red;
Score 0.5: There was a suspicion of skin roughness-generation; and
Score 0: There was not observed any reaction.
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CA 02610778 2007-11-30
Regarding the foregoing evaluation criteria, the skin roughness-generation
was carried out on the basis of the score obtained by summing the results
obtained for 10 subjects and therefore, the lower the score obtained, the
higher
the skin roughness-inhibitory effect of the candidate composition. The border
line
for judging whether each composition could be acceptable was set at the level
of
"score 5".
Test for Stability to Dilution
There was prepared hard water (a liquid obtained by diluting 0.0757g of
calcium chloride dihydrate with distilled water to a total volume of one
liter;
German hardness: 3 deg.; Ca hardness: 54 ppm; see, for instance, JIS K 2221
"Cutting oil, Test for Stability to Emulsification"), each candidate
composition
was diluted with the hard water thus prepared to thus give a 5% diluted
composition and then the diluted composition was visually observed immediately
after the dilution and after 24 hours from the dilution. The evaluation
standards
are as follows:
0: Acceptable; The composition was uniformly dissolved and free of any
separation and the formation of any creamy layer;
Em: Unacceptable; There were observed the separation of the composition and
the formation of a creamy layer.
Test for Cutting property (Cutting Ability)
There was used, as a specimen, a material of an aluminum alloy (AC8B-
T6, 300X200X30 mm, HRB60), then a prepared hole of 0 5.45, blind hole were
22
CA 02610778 2007-11-30
formed and the test for inspection of cutting property was carried out using a
tap
of M6 (New Roll Tap available from OSG Company) under the following
conditions:
Cutting Speed: 10 m/min; Feed: 1 mm/rev.; Cutting Length: t = 17 mm (blind
hole); "N" Number: 5.
The diluted metal-processing oil composition was supplied at a feed rate of
6 L/min.
Cutting property was evaluated on the basis of the evaluated tapping
torque value thus obtained and on whether the cutting tool was broken or not.
The evaluation standards are as follows:
O: Acceptable; tapping torque: not more than 500 N- cm;
x: Unacceptable; there was observed welding of the cutting tool (processing of
the material was impossible).
The results thus obtained are summarized in the following Tables 4 to 6.
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CA 02610778 2007-11-30
Table 4:
1 2 3 4 5 6 7 8
Putrefaction
resistance
After 7 days
General no no no no no no no no
bacteria
Mold no no no no no no no no
Yeast no no no no no no no no
Anaerobic no no no no no no no no
bacteria
After 14 days
General no no no no no no no no
bacteria
Mold no no no no no no no no
Yeast no no no no no no no no
Anaerobic no no no no no no no no
bacteria
Skin 2.5 2.5 2.5 3.0 2.5 2.5 2.5 2.0
roughness-
eneration
Overall
'ud ment
Putrefaction 0 0 0 0 0 0 0 0
resistance
Skin 0 0 0 0 0 0 0 0
roughness-
eneration
Cutting 0 0 0 0 0 0 0 0
pro ert
Dilution 0 0 0 0 0 0 0 0
stability
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CA 02610778 2007-11-30
Table 5
9 10 11 12 13 14 15 16
Putrefaction
resistance
After 7 days
General no no no no no no no no
bacteria
Mold no no no no no no no no
Yeast no no no no no no no no
Anaerobic no no no no no no no no
b acteria
After 14 days
General no no no no no no no no
bacteria
Mold no no no no no no no no
Yeast no no no no no no no no
Anaerobic no no no no no no no no
bacteria
Skin 4.0 3.0 5.0 4.5 2.5 2.5 2.5 2.5
roughness-
eneration
Overall
judgment
Putrefaction 0 0 0 0 0 0 0 0
resistance
Skin 0 0 0 0 0 0 0 0
roughness-
generation
Cutting 0 0 0 0 0 0 0 0
property
Dilution 0 0 0 0 0 0 0 0
stability
CA 02610778 2007-11-30
Table 6
17 18 19 20 21 22 23 24 25 26 27 28
Putrefaction
resistance
After 7 days
General no no no no no no no no no no no no
bacteria
Mold no no L no no no no no L no no no
Yeast 104 no 103 no no no 104 no 104 no no no
Anaerobic no no no no no no no no no no no no
bacteria
After 14 days
General no no no no no no no no no no no no
bacteria
Mold no no H no no no no no H no no no
Yeast 106 no 105 no no no 106 no 105 no no no
Anaerobic no no no no no no no no no no no no
bacteria
Skin 2.5 6.0 2.0 5.5 5.5 5.5 3.0 6.0 2.5 6.5 6.5 6.0
roughness-
eneration
Overall
judgment
Putrefaction x 0 x 0 0 0 x 0 x 0 0 0
resistance
Skin 0 x 0 x x x 0 x 0 x x x
roughness-
generation
Cutting 0 0 0 0 0 0 0 0 0 0 0 0
property
Dilution 0 0 0 0 x 0 0 0 0 x x 0
stability
The results listed in Tables 4 to 6 clearly indicate that the water-soluble
cutting oils (stock solution) according to the present invention prepared in
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CA 02610778 2007-11-30
Examples 1 to 16 were found to be excellent in all of the characteristic
properties
examined, or the putrefaction resistant property, the skin roughness-
inhibitory
effect, the cutting property and the stability to dilution.
27